Petroleum oxidation products and their utilization



Patented June 16, 1936 UNITED I STATES PATENT "OFFICE PETROLEUMOXIDATION PRODUCTS AND THEIR UTILIZATION 1 Carleton Ellis, Montclair, N.5., assignor to Ellis- Foster Company, a corporation of New Jersey NoDrawing.

Application January 29, 1925, Serial No. 5,634

' 24 Claims. -.(.c|. zoo-2) This invention relates to petroleumoxidation products and to their utilization and relates especially toproducts obtained in the oxidation and/or cracking of, heavy oils suchas petroleum oil, shale oil, asphalt, gilsonite and the like. I

Theobject of the invention is to render petroleum more generallyavailable for diverse in- In said patent and patent application I have.-referred to'the production of aldehydes by the xid i n i petroleum andalso to the derivation 20 oiresinous substances by the-process describedtherein.

The present invention is particularly concerned with the evaluation orutilization of petroleum aldehydes,as the aldehydic bodies obtained by25 oxidation may be termed, and also in rendering more useful theresinous substances obtained in the oxidizing operation and in laterrefining steps. The materials required in the present inventiontherefore may be made in accordance with the 30 disclosures oi Patent1,517,968, or Serial 743,453. Analogous products may be made by blowingair through oil especially when under pressure and heated to a suitabletemperature. For example gas oil at a pressureof 300 lbs.,' temperature385" 35 C. to about 400 C., may be blown with preheated air and theproducts of oxidation collected, preferably under pressure. A condensateis obtained in two layers, one consisting of more or less volatilehydrocarbons, and an aqueous layer 40 containing petroleum aldehydes andvarious water soluble'bodies. The aqueous condensate and also washingsobtained from the hydrocarbon condensate may be distilled to separatelight fractions containing acetaldehyde and higher alde- 45 hydes.Further distillation yields various solvents. By purifying these throughtreatment with caustic soda and re-distillation resinous or gummymaterial is obtained. This resinous ma,- terial may be used inaccordance with the present 50 invention in the same manner as the resindescribed in Patent 1,517,968 and in specification of Serial 743,453.For example in the latter speci flcation, page 7, I state that bycarrying out the oxidation at a temperature of 300 to 400 C. alde- 65hydes and fatty acids are obtained. A small hydes may be employedinvarious ways,

amount of formaldehyde sometimes is produced but higher aldehydes,especially acetaldehyde, predominate. The treatment of the aqueoussolution containing aldehydes and acids is prefer-- ably as follows: Ifthe aldehyde is desired in the 5 freestate the solution is renderedneutral with caustic soda and distilled with steam. The aldehyde iscarried over and the aqueous solution becomes practically odorless. Thehigher aldeexample they may be made to react with, or in the presence ofcaustic soda, to form resinous substances. In one case a resin of thissort produced from kerosene as described in Serial 743,453 was obtainedin the form of a light brown' powder which when melted was a resinoussubstance. Aldehydes obtained by the process are capable ofpolymerization and condensation (Serial 743,453, page 10) When causticalkali is employed in the refining operation any organic acids obtainedwill form salts which can be thus separated from the solvents andaldehydes and the organic acids subsequently liberated by treatment witha mineral acid and distillation or separation in any othersuitablemanner. The gum or resin obtained in the alkali treatment byitself isof little value, it isusually a reddish product ranginginconsistency from a sticky gummy mass to a resin of more brittlequalities. Simple heating usually serves to harden it butat the sametime tends to deepen the' color. For some purposes the color of theresin should be preserved as dark colored or black products areundesirable.

It may be noted that petroleum resins have been derived in various waysbut these have in the past usually been obtained from acid sludge andresidues such as pitch, asphalt and the like and generally are black,brittle, ill-smelling substances which are of no practical value in mak-40 ing products contemplated in accordance with the present invention.Resins have been obtained from cracked petroleum by polymerizingdioleflns and the-like but these in the main are hydrocarbon resinswhile the resin particularly utilized in accordance with'the presentinvention, in its preferred form is one obtained through the agency ofan oxidation process and the gummy or resinous product obtainedhereunder contains a considerable amount of oxygen in combination andhas a reactivity substantially difl'erent from the relatively inerthydrocarbon resins. It may be termed reactive oxygenated pertoleum resinto distinguish it from pitches and tars cusfor 10 tomarily obtained inthe various operations of refining petroleum oil.

For example equal parts of phenol and such reactive gum were heated inthe presence of a small amount of hydrochloric acid. A resinous solidwas obtained which when mixed with about 10 per cent ofhexamethylenetetramine was found to set or harden on heating. The uniontherefore of the phenol with the reactive oxygenated petroleum resinyielded a resinous derivative reactive with hexamethylenetetramine.

In the oxidation of petroleum a considerable amount of phenoloid bodiesare derived and such bodies may be permitted to react with the reactiveoxygenated petroleum resin to make resinous derivatives of an analogouscharacter. These in turn may be given more rapid thermosetting qualitiesby the addition of hexamethylenetetramine. The addition of the lattersubstance is however not essential as such a resinous complex may behardened by baking. Thus molded articles may be made from this resinouscomplex by cold pressing andthe molded articles then baked carefullyuntil hardened to the desired degree.

The resins thus obtainable may be used in hot pressing or hot moldingoperations as well as in cold molding. They may be used alone in orderto get clear resinous hard products or they may be mixed with the usualfillers such as are now employed inthe rubber, paint, linoleum andsynthetic resin industries; a list of which need not be given herein indetail.

Such resins also may be mixed with other natural or synthetic resinssuch as acetone- !ormaldehyde resin, urea-formaldehyde resin,phenol-formaldehyde resin, phthalic glyceride resin. salicylic phthalicglyceride resin, rosin phthalic glyceride resin, benzoic zlyceride resinand the like to modify its properties in various desired ways.

Blown asphalts and other resins of petroleum origin. but not having thereactive properties of the oxygenated petroleum resin of the presentinvention, likewisemay be added in some cases but in general are notrecommended because of the tendency to brittleness, discoloration, etc.

The present invention has for its object to obtain from petroleum bycombination of the various substances obtained by an oxidation step orby the employment of such substances along with substances obtained fromother sources, a high grade resin capable of being used in fabricatedproducts of high quality. For example molded articles to serve aselectrical insulation, for ornamental purposes, as tool handles,umbrella handles, smokersutensils, billiard balls, bed casters andnumerous other articles of this character; likewise in the form oflacquers and enamels, as varnishes for coating wood and metaliicsurfaces. In this case the varnish may be of a kind which will befinished simply by drying of the solvent or it may be of the enamel typewhich requires baking to accomplish-the requisite hardening effect.Solutions may be made of the resin of the present invention which may beemployed for impregnating cloth, paper or other tissue, the impregnatedmaterial being pressed together to build up blocks or sheets ofappropriate toughness and strength to serve as radio panels, for makinggears and many other uses where a tough hard product is required.

The reactive oxygenated petroleum resin may be combined withacetaldehyde and higher aldehydes obtained in the oxidizing operation asfor example by heating with caustic alkali; or the reactive oxygenatedpetroleum resin may be reacted with the phenoloid bodies obtained insaid oxidizing operation; or the reactive oxygenated petroleum resin maybe treated with acetaldehyde and higher aldehydes in the presence ofsaid phenoloid bodies, or in some cases phenol, cresol, xylenol or otherlike substances derived from others sources may be introduced into thereaction mixture to supplement conversion to a resin of desiredcharacteristics.

Since the proportions of resin, aldehydes and phenoloid bodies obtainedin oxidation may be expected to vary with different kinds of crude oilmaterial employed and since such proportions may not always be thosedesired for use in making finished resins,.suitable for fabricatedproducts there may be an excess of some of the products which may bediverted to other uses. Also it may be necessary as indicated above todraw on outside sources for certain of the raw materials required inmaking special products.

For example furfural may be employed in building up a resinous compositein accordance with the present invention and this substance may beacquired from an outside source. Phenols, naphthols and the like may besecured in a similar manner in order to obtain the requisite proportionof ingredients for special purposes.

In general however the products of the present invention whetherappearing as resins, molded products, lacquers or varnish coatings,laminated pressboard, laminated cloth and the like contain essentially aresin of petroleum derivation. Thus the product may be derived directlyfrom the reactive oxygenated petroleum resin or by combining it withvarious other substances as indicated or it may be made by reacting withacetaldehyde derived from the oxidation of petroleum, which acetaldehydeis combined with phenol or phenolic bodies, naphthols and the like, thereaction preferably being carried out in the presence of an acidcatalyst to form a resin. Or a mixture of acetaldehyde and higheraldehydes for example the crude petroleum aldehyde distillate may becombined with phenolic bodies in the presence of an acid catalyst toyield a resin. As very little formaldehyde is obtained in the processunder normal conditions it is likewise possible when formaldehydeobtained by the process is insufficient in quantity to secureformaldehyde from other sources and react the formaldehyde with thereactive oxygenated petroleum resin and phenol to produce a compositeresinous product. In like manner acetaldehyde or a mixtureofacetaldehyde and higher aldehydes obtained in the petroleum oxidationprocess may be reacted with phenol and formaldehyde to obtain a complexresin. Phenoloid bodies obtained in the operation may be employed and ifdesired these may be supplemented by the addition of phenol or cresolobtained for example from coal tar. The phenoloid bodies from petroleummay be entirely replaced by such substances in some cases.

As an example parts by weight of soft sticky gum resin derived bypetroleum oxidation was incorporated with 50 parts of phenol and 12parts of acetaldehyde of petroleum origin. Approximately 3 parts byweight of concentrated hydrochloric acid were added. The mixture washeated under a reflux condenser for approximately 1 registering 26inches. I

molds and pressed at a temperature of 160 C.

. tents of the vessel heated to 150 C.

The secondary resin thus obtained was heated to approximately 150 C. toeliminate water and hydrochloric acid. v The dry resin was dissolved inapproximately an equal weight of alcohol and was incorporated with woodflour equal in weight to the resin and the mixture was dried in a vacuumdryer, the temperature being raised gradually to C. with the gauge ofthe dryer Composition was, put into with the gauge of the pressregistering 1000 pounds. Setting took place rapidly and articlesproperly cured were obtained in less'than 5 minutes time. Sticking tothe mold is likely to occur with resins made from the petroleumaldehydes and the addition of 1 or 2 per cent of a waterinsoluble soapsuch as aluminum palmitate or. zinc stearate may be required to overcomethis v r I employedin whole, or in part. Employing the 12 parts byweight of the primary resin,

: parts of acetaldehyde of petroleum origin,

50 parts of phenol and approximately 3 parts of concentrated aqueoushydrochloric acid were heated together for an hour under a refluxcondenser, the temperature reaching approximately 105 C. The condenserwas removed and the conpotassium carbonate and 12 partsof furfural whatby heating to C. This resin was dis solved in alcoholhexamethylenetetramine and wood flour added as in the foregoing exampleand the composition dried and molded in like manner.

It hardened well in the mold although notfquite so rapidly as theproduct of the preceding example 1 and was found to flow well when hotpressed.

To recapitulate the-invention'is concerned with the art of renderingpetroleum more generally I available for diverse industrial purposesthan'those heretofore commonly recognized. In' one form the invention isconcerned with oxidizing petroleum to generate aldehydic substancesconverting some part at least of the latter into resinous material andemploying said resinous material as a binder inplastics, in makinglaminated fibre and electrical insulation as well as varnishes,lacquers, enamels and the like. The invention involves in one form theresiniflcation process which comprises reacting on the phenoloids ofoxidized petroleum with the aldehydes of oxidized petroleum. Thealdehydes may be the mixture of such compounds as normally obtain or maybe special fractions or even the substantially pure individual aldehyde.The reaction may be carried out to advantage in the presence of acatalyst such as an alkali or an acid and preferably an acid. The resinthus obtained may be admixed with fillers and molded by hot pressing orcold molding methods. When hot molding methods are employed it may beadvantageous to include in the molding composition a few per cent ofhexamethylenetetramine. When the oxidation process is such that asubstantial proportion of acetaldehyde is obtained this substance ..inthe pure or prising essentially acetaldehyde.

. mercial value.

5 parts of crude state may be employed so that the process involvedwould be that of reacting on a phenolic I body with acetaldehyde ofpetroleum origin or with the aldehydes of oxidized petroleum com--v Theprocess 5 however is not limited to the phenoloids of oxidized petroleumas thesemay be replaced wholly or in part by phenol, cresol, xylenol andother similar compound. Another modification is that of employingreactive oxygenated petroleum resin 10 or gum in making a resinousmaterial of com- The crude petroleum resin of this character is byitself a relatively low grade product but by subjecting it to theactionof a phenoloid body. such as substances of this kind 15 obtainedin petroleum oxidation, carrying out the reaction in the presence ofacatalyst, espe-. cially a mineral acid, resinsof commercial signiflcanceare obtained. In addition to phenoloid bodies from this source phenols,cresols,.xylenols 20 and the like from coal tar or other source may bematerial by itself has the property of hardening 0 I for setting whenheated and the reaction is facilitated by adding hexamethylenetetramine,yielding for example a molding. composition comprisinga heat-settingresinof petroleum origin usually'incorporated with filling material.spe- 3 ciflcally resins may be preparedfrom such substances as ortho,'meta or para cresol or xylenol -and an aldehyde. of petroleum orgin.Usingaldev hydic material originating in this manner certain impuritiesor by-products'often may be present 40 which accelerate the reaction andtend to give a harder and stronger resin. In other cases the impuritiesmay have valuable fluxing or plasticizing properties. The latter effectis facilitated by the employment of hexamethylenetetramine 45 triphenoland the like. 'Varnishes may be made by dissolving any of the solubleforms of the herein described resins in a solvent,"for example a mixtureof benzol and alcohol. Still another modification is that of reacting ona portion at 50 least of the oxidized products of petroleum with aneutralizing agent to form salts of organic acids and separatingaldehydic substances therefrom.

Such substances then may be converted to resins in the manner hereindescribed. Instead of neu- 55 tralizing an excess of alkali for examplecaustic soda" or its equivalent, caustic potash, may .be

employed to induce a primary. resinification. Sucha primary resin of anoxygenated character is normally reactive and from it secondary resins60 are obtainable by reaction with phenol, with or without aldehydessuch as formaldehyde, butyl aldehyde, furfural and the like. Theproduction of secondary orcommercially useful resins from the crudeprimary resin or gum may be carried 65 out in more than one stage as forexample by reacting on the gum with phenol in the presence of an acidcatalyst and subsequently reacting on that product with furfural in thepresence of an alkaline catalyst. 7

By the term phenoloid is meant a material which resembles or reacts likea phenol in resinifying reactions.

By the term reactive oxygenated petroleum resin ismeant a material ofresinous nature ob- 75 tained in the oxidation of petroleum and relatedhydrocarbons, which resinous material contains a considerable amount ofoxygen in combination, and exhibits a pronounced reactivity toward suchmaterials as aldehydes, phenols and phenoloid bodies, etc.

What I claim is:-

1. The resiniiication process which comprises reacting on the phenoloidsof oxidized petroleum with the complex, mixed aldehydes of oxidizedpetroleum.

2. The resiniiication process which comprises reacting on the phenoloidsof oxidized petroleum with the complex, mixed aldehydes of oxidizedpetroleum comprising essentially acetaldehyde.

8. The resiniiication process which .comprises reacting on thephenoloids of oxidized petroleum with the complex, mixed aldehydes ofoxidized petroleum in the presence of a catalytic substance.

4. The resiniilcation process which comprises reacting on the phenoloids'of oxidized petroleum with the complex, mixed aldehydes of oxidizedpetroleum in thepresence of an acid catalyst.-

5. The resiniiication process which comprises subjecting reactiveoxygenated petroleum resin to the action of aldehydes from oxidizedpetroleum.

6. The resiniilcation process which comprises subjecting reactiveoxygenated petroleum resin 'to the action of aldehydes from oxidizedpetroleum comprising essentially acetaldehyde.

7. The resinincationprocess which comprises subjecting reactiveoxygenated petroleum resin to the action of a'phenolo'id body.

8. The resiniiication process which comprises subjecting reactiveoxygenated petroleum resin to the action of a phenoloid body in thepresence of a catalyst.

9. The resiniflcation process which comprises subjecting reactiveoxygenated petroleum resin to the action of a phenoloid body in thepresence of an acid catalyst.

10. The resiniiication process which comprises subjecting reactiveoxygenated petroleum resin to the action of a phenoloid body in thepresence of an acid catalyst and incorporating with the resignifledmaterial a small proportion of hexamethylenetetramine.

. 11. The resiniilcation process which comprises subjecting reactiveoxygenated petroleum resin to the action of at least twoaldehydicsubstances.

12. The resiniflcation process which comprises subjecting reactiveoxygenated petroleum resin to the action of at least two aldehydicsubstances in the presence of a phenol. I

13. A resinous body prepared from reactive oxygenated petroleum resin,phenol and acetalde- Me.

14. A resinous body prepared from reactive oxygenated petroleum resin, aphenolic body and aldehydes from oxidized petroleum.

aoeaooa 15. A resinous body prepared from reactive oxygenated petroleumresin, phenol, aeetaldehyde and another aldehyde.

16. A resinous body prepared from reactive oxygenated petroleum resin,phenol, a. plurality 6 of aldehydes and hexamethylenetetramine.

1'7. The process which comprises heating reactive oxygenated petroleumresin with phenol in the presence of an acid catalyst, adding aqueousformaldehyde and continuing the heating.

18. The process which comprises reacting on a phenolic body and reactiveoxygenated petroleum resin with acetaldehyde of petroleum origin in thepresence of an acid catalyst.

19. The process which comprises heating a reactive oxygenated petroleumresin with phenol in the presence of an acid catalyst and furi'ural inthe presence of an alkaline catalyst.

20. In the manufacture of phenolic condensation products, the stepscomprising causing a phenolic body to react with an oil mainly of theallphatic type and containing hydrocarbon derivatives of difierentmolecular weights having an aldehyde base to form an initialcondensation product and thereafter heating the same to form a hardinfusible insoluble synthetic resin.

21. In the manufacture of phenolic condensation products, the stepconsisting of reacting with a phenolic body an alkali resinifled mixtureof oxidized hydrocarbon derivatives mainly of the aliphatic typeresulting from a vapor or gaseous phase reaction between carbon hydrogenand oxygen containing materials, said product containing bodies ofdiiferent molecular weights having aldehyde properties.

22. In the manufacture of phenolic condensation products, the stepconsisting of treating with a phenolic body an alkali resinifiedfraction of a liquid mixture of oxidized hydrocarbon derivatives mainlyof the aliphatic type containing 40 bodies having aldehyde propertiesformed by vapor or gaseous phase reaction between carbon, hydrogen andoxygen containing materials.

- 23. As a new article of manufacture, a hard infusible insolublesynthetic resin formed by the reaction between phenolic bodies and amixture of resin acids derived from oxidized hydrocarbonderivativesformed by vapor or gaseous phase catalytic reaction ofcarbon-hydrogen-oxygen containing gases, said acids being of diiferentmolecular weights.

24. As a new article of manufacture, a hard infusible insolublesynthetic resin formed by the reaction between a phenolic body and anoxidized hydrocarbon mixture formed by the vapor or gaseous phasereaction of hydrocarbon and oxygen containing vapors or gases, saidderivatives containing bodies of diiferent molecular weights havingaldehyde properties.

CARLE'IDN ELLIS.

